DE2705995A1 - PYRIDAZINONE (THIONO) PHOSPHORUS (PHOSPHONE) ACID ESTER, METHOD FOR THEIR PRODUCTION AND USE AS INSECTICIDES AND ACARICIDES - Google Patents

Description

PyridazinonC thiono) phosphorus (phosphonic) acid ester, process for their preparation and their use as insecticides and acaricides

The present invention relates to new pyridazinone (thiono) -phosphor ^ phosphonic) acid esters, a process for their preparation and their use as insecticides and acaricides.

It is already known that Pyridazinonthionophosphor- or -phosphonates, for example, OO-diethyl-O-CL-phenyl-ltö-dihydropyridaz (6) one (3) Y3d-thionopho "phorsäureester ^una O-ethyl-0-D · - phenyl -1,6-dihydro-pyridaz (6) one (3) yi] -thionoethane phosphonic acid esters, are distinguished by an insecticidal and acaricidal activity (cf. US Pat. No. 2,759,937 and Belgian Pat. No. 844,857).

There were new pyridazinon (thiono) phosphorus (phosphonic) acid esters of the formula

(D

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found,

in softer

R is alkyl, R ^{1 is} alkyl or alkoxy, R ^{2 is} haloalkyl and

X and Y are identical or different and represent oxygen or sulfur.

These new compounds are characterized by strong insecticidal and acaricidal properties.

It was also found that the pyridazinone (thiono) phosphorus (phosphonic) acid ester of the formula (I) can be obtained if (thiono) phosphorus (phosphonic) acid ester halides of the formula

ΐ / OR
HaI-P ( ₁ (II)

in which R, R ¹ and X have the meaning given above and Hal is halogen, preferably chlorine,

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with _3- hydroxy-l, 6-dihydropyridazinones of the formula

(III)

in which

2 R and Y have the meaning given above,

optionally in the form of the alkali, alkaline earth or ammonium salts or optionally in the presence of an acid acceptor and optionally reacted in the presence of a solvent.

Surprisingly, the pyridazinone (thiono) phosphorus (phosphonic) acid esters according to the invention show better insecticidal properties and acaricidal action than the corresponding previously known pyridazinonthionophosphorus or phosphonic acid esters of analogous constitution and the same direction of action. The products according to the present invention thus represent a real enrichment of the Technology.

If, for example, O-sec-butyl-ethanephosphonic acid ester chloride and 1- | ~? - (1 »1.2,2-tetrafluoroethylthie-phenyl) J-1,6-dihydro-3-hydroxypyridazinone (6) are used as starting materials, so the course of the reaction can be represented by the following equation:

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C ₂ H ₅

270599b

^0H

S / O ^ Hg-sec. ^ _n Cl-P _x ^ ⁺ υ L

ACF ₂ -CHF ₂

Acid-

The starting materials to be used are defined by the formulas (II) and (III) generally defined. Preferably, however, it says

R for straight-chain or branched alkyl with 1 to 6, especially 1 to 4 carbon atoms,

R stands for straight-chain or branched alkyl or alkoxy with

1 to 3, especially 1 to 3 »carbon atoms each Alkyl or alkoxy radical,

R for straight-chain or branched haloalkyl with 1 to 4, in particular 1 or 2, carbon atoms, and halogen therein preferably denotes fluorine or fluorine and chlorine,

X for sulfur and Y for oxygen or sulfur.

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The (thiono) phosphorus (phosphonic) acid ester halides (II) to be used as starting materials are known. [ The following are specifically mentioned as examples: 0,0-dimethyl-, 0,0-diethyl-, 0,0-di-n-propyl-, 0,0-di-isopropyl-, O-methyl-0-ethyl -, O-methyl-0-n-propyl-, O-methyl-0-iso-propyl-, O-methyl-0-n-butyl-, O-methyl-0-isobutyl-, O-methyl-O- sec-butyl-, O-ethyl-0-n-propyl-, O-ethyl-0-iso-propyl-, O-ethyl-0-n-butyl-, O-ethyl-0-sec-butyl- , O-ethyl-0-iso-butyl, on-propyl-0-butyl or O-iso-propyl-0-butylphosphoric acid diester chloride and the corresponding thiono analogs and O-methyl, O-ethyl, on-propyl , O-iso-propyl, on-butyl, O-iso-butyl and O-sec-butyl methane or ethane, n-propane and iso-propane phosphonic acid ester chloride and the corresponding thiono analogs.

The 3-hydroxy-1,6-dihydro-pyridazinones (III) to be used as starting materials have not yet been described, but can be prepared by processes known from the literature.

Examples are: 1- (4-trifluoromethoxyphenyl) -, 1- (A-trifluorothiophenyl) -, 1- (3-trifluoromethoxyphenyl) -, 1- (3-trifluoromethylthiophenyl) -, 1- (4-Difluoromethoxyphenyl) -, 1- (4-Difluoromethylthiophenyl) -, 1- (3-difluoromethoxyphenyl) -, 1- (3-difluoromethylthiophenyl) -, 1- [4-0-, 1,2,2-tetrafluoroethoxy) phenyl] -, 1 - (^ - (1,1,2,2-tetra fluoroethylthio) phenyl | -, l - [> - (l, l, 2,2-tetrafluoroethoxy) phenyl] -, 1-C3- (1 »1» 2 ₁ 2-tetrafluoroethylthio) phenyl} -. 1-0 »" (1,1,2-trifluoro-2-chloroethoxy) -phenyl] -, 1- [4- (1,1,2 ^ trifluoro-2-chloro-ethylthio) -phenyi3-r, l- [3- (l »l» 2 -trifluoro-2-chloroethoxy) -phenyl] - or lp- (ll, 2-trifluoro-2-chloroethylthio) -phenyl] -l, 6-dihydro-3-hydroxypyridazinone (6 ).

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The process for the preparation of the compounds according to the invention is preferably carried out using suitable solvents or diluents. Practically all inert organic solvents can be used as such. These include in particular aliphatic and aromatic, if appropriate chlorinated hydrocarbons such as benzene, toluene, xylene, gasoline, methylene chloride, chloroform, carbon tetrachloride, Chlorobenzene, or ethers, e.g. diethyl and dibutyl ethers, dioxane, also ketones, for example acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, and also nitriles, such as Aceto- and propionitrile.

All customary acid binders can be used as acid acceptors. Alkali carbonates have proven particularly useful and alcoholates, such as sodium and potassium carbonate, sodium and potassium methylate or ethylate or potassium tert-butoxide, furthermore aliphatic, aromatic or heterocyclic amines, for example triethylamine, triethylamine, dimethylaniline, dimethylbenzylamine and pyridine.

The reaction temperature can be varied within a relatively wide range. Generally one works between O and 120 ° C, preferably at 15 to 60 ° C.

The reaction is generally allowed to proceed under normal pressure.

To carry out the process, the starting components are preferably used in equivalent proportions. A

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Excess of one or the other component brings no significant advantages. The reaction components are generally combined in one of the solvents indicated and usually at elevated temperature to complete the Reaction stirred for one or more hours. The reaction solution is then cooled, shaken out with water and the organic phase is worked up as usual by drying and distilling off the solvent.

The new compounds are mostly in the form of oils that in some cases cannot be distilled without decomposition, however by so-called "partial distillation", i.e. by prolonged heating under reduced pressure to moderately elevated temperatures of the last volatile components are freed and cleaned in this way. The refractive index is used to characterize them. Some compounds are obtained in crystalline form and are characterized by their melting point.

The 3-hydroxy-1,6-dihydropyridazinones of the formula (III) which have not previously been described can be used according to known methods Process. For example, you can use the corresponding haloalkoxy or haloalkylthioaniÜne of the formula (IV)

.2

(IV)

in which Y and R have the meaning given above,

diazotize, convert the diazonium compound into hydrazine by adding reducing agents such as tin (II) chloride and converting this with maleic anhydride to the desired product.

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As already mentioned several times, the pyridazinone (thiono) phosphorus (phosphonic) acid esters according to the invention are distinguished excellent insecticidal and acaricidal effectiveness. They work against pests of plants, hygiene and stored products. With low phytotoxicity, they both have a good one Effect against sucking as well as eating insects and mites.

For this reason, the compounds according to the invention Successfully used in crop protection as well as in the hygiene and stored product protection sector as a pesticide will.

The active ingredients are suitable if they are well tolerated by plants and favorable warm-blooded toxicity for the control of animal pests, especially insects and arachnids, which occur in agriculture, forests, in the protection of stored products and materials as well as in the hygiene sector. You are against normally sensitive and resistant species as well as effective against all or individual developmental stages. To the above mentioned Pests include:

From the order of the Isopoda, for. B. Oniscus asellus, Armadilli-

dium vulgare, Porcellio scaber.

From the order of the Diplopoda, for. B. Blaniulus guttulatus. From the order of the Chilopoda, for. B. Geophilus carpophagus, Scutigera spec. From the order of the Symphyla z. B. Scutigerella Immaculata. Aue of the order of Thysanura z. B. Lepisma saccharine. From the order of the Collembola, for. B. Onychiurus armatus. From the order of the Orthoptera z. B. leaf orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica,

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Acheta domesticus, Gryllotalpa spp., Locusta migratoria

migratorioides, Melanoplus differentlaIls, Schietocerca gregaria.

From the order of the Dermaptera, for. B. Forficula auricularia. From the order of the Isoptera, for. B. Retlculitermes spp. From the order of the Anoplura, e.g. B. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp ,, Linognathus spp. From the order of the Mallophaga, e.g. Trichodectes spp., Damalinea From the order of the Thysanoptera, e.g. Hercinothrips femoralis, Thrips tabaci. From the order of the Heteroptera, e.g. Eurygaster spp., Dysdercus intertnedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp. From the order of the Homoptera, e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum. Aphis gossypii,

Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, proceeds oma lan ige rum, Hyalopterus arundinis, Macro siphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidlella aurantii, Aspidiotus hederae, Pseudococcus spp.,

Psylla spp ..

From the order of the Lepidoptera, for. B. Pectinophora gossypiella,

Bupalus piniarius, Cheinatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella naculipennls, Halaco8ooa neustria, Euproctis chrysorrhoea, Lymantria spp "Bucculatrix thurberiella, Phyllocnlstis citr« lla _f Agrotla spp., Euxoa spp., Feltla spp., Bariaa insulana, Heliothls app ., Laphygma exigua, Maaestra brassicae, Panolis flaamea, Prodenia litura, Spodoptera spp., Trichopluaia ni,

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Carpocapsa pomonella, Pieris spp., ChiIo 3pp., Pyrausta nubilalis, Epheetla kuehnlella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumlferana, Clysia ambiguella, Homona magnanima, Tortrlx viridana. From the order of the Coleoptera ζ. B. Anoblum punctatum, Rhlzopertha dominlca, Bruchldius obtectus, Acanthoscelides ob tea tue, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Fnaedon cochleariae _f Olabrotica spp. , Psylliodes chrysocephala, Epllachna varivestis, Atomarla spp., Oryzaephllua surinamensis, Anthonomus spp., Sitophllus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus sp. Lyctus spp., Meligethes aeneus, Ptlnus spp., Niptus hololeucus, Gibblum psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderue spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

From the order of the Hymenoptera, for. B. Dlprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp. From the order of the Diptera, for example, Aedes spp. Anopheles spp., Culex spp., Orosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Hyppobosca spp ., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oxclnella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacue oleae, Tipula paludosa.

From the order of the Siphonaptera, for example Xenopsylla cheopis and Ceratophyllus spp. .

From the order of the Arachnida, e.g. Scorpio maurus, Latrodectus mactans.

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270599b

From the order of the Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..

The active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, suspension emulsion concentrates, seed powders, active ingredient-impregnated natural and synthetic substances, very fine encapsulations in polymeric substances and in coating compounds for seeds, also in formulations with burning charges, such as smoking cartridges, cans, spirals, etc. as well as ÜLV cold and warm fog foils.

These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, i.e. liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, i.e. emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, it is also possible, for example, to use organic solvents as auxiliary solvents. The following liquid solvents could essentially be considered: aromatics, such as xylene, toluene, or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, eg petroleum fractions, alcohols such as butanol or Glycol and their ethers and esters, ketones such as acetone, methyl

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2706995

AS

Ethylene ketone, methyl isobutyl ketone or cyclohexanone, strong polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; Liquefied gaseous extenders or carriers are liquids that which are gaseous at normal temperature and under normal pressure, e.g. Aeroaol Trelbgases, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carrier materials: natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, Montmorillonite desolate diatomaceous earth and synthetic rock flour, such as highly dispersed silica, aluminum oxide and Silicates; as solid carriers for granulates: broken and fractionated natural rocks such as Calcite, marble, pumice, sepiolite, dolomite and synthetic granules made from inorganic and organic flours as well Granules of organic material such as sawdust, coconut shells, corn on the cob, and tobacco stalks; as emulsifying and / or foam-generating agents: non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, Alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates; as dispersants: e.g. lignin sulphite waste liquors and methyl cellulose.

There can be adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular in the formulations or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate.

Dyes such as inorganic pigments, e.g. iron oxide, titanium oxide, ferrocyan blue and organic dyes, such as alizarin, azo-metal phthalocyanine dyes, and

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Trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90 %.

The active ingredients according to the invention are used in the form of their commercially available formulations and / or the use forms prepared from these formulations.

The active ingredient content of the use forms prepared from the commercially available formulations can vary within wide limits. The active ingredient concentration of the use forms can be from 0.0000001 to 100 % by weight of active ingredient, preferably between 0.01 and 10% by weight.

They are used in a customary manner adapted to the use forms.

When used against hygiene pests and pests of stored products, the active ingredients are distinguished by an excellent residual effect on wood and clay as well as good alkali stability on limed substrates.

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Example A Plutella test

Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amount Solvent and the specified amount of emulsifier and dilute the concentrate with water to the desired Concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the active ingredient preparation and are populated with caterpillars Cabbage moth (Plutella maculipennis).

After the specified times, the destruction is determined in % . 100 % means that all the caterpillars have been killed; 0 % means that none of the caterpillars have been killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table A below:

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Table A (plant-damaging insects)

Plutella test Active ingredients

Active ingredient concentration tion in%

Degree of destruction in% after 3 days

OP (OC ₂ H ₅ )

0.01 O, OO1

100 0

-OCF.

0.01 O, OO1

1OO 1OO

OCP.

0.01 001

1OO 90

S. O-P

Il

-C ₂ H ₅

-OCF-

0.01 0.001

100 100

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Tabel

(Continuation)

(plant-damaging insects) Plutella test

Active ingredients

Active ingredient concentration tion in%

Degree of destruction in% after 3 days

(16)

OCF ₂ -CHF ₂

0.01 0.001

100 90

-SCF.

(19) 0.01 0.001

100 100

(11) 0.01 0.001

100 100

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ao

Example B.

Tetranychus test (resistant)

Solvent: 3 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

Mixed to produce an appropriate preparation of active ingredients 1 part by weight of active ingredient with the specified amount of solvent and the specified amount of emulsifier and dilutes the concentrate with water to the desired concentration.

The preparation of the active compound is used to produce bean plants (Fhaseolus vulgaris), which differ greatly from all stages of development of the common Spider mite or bean spider mite (Tetranychus urticae) are infected, sprayed until dripping wet.

After the specified times, the destruction is determined in % . 100% means that all spider mites have been killed; 0 % means that no spider mites have been killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table B below:

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Tabel

Active ingredient «

(plant-damaging mites) Te tranychus-Tes t

Active ingredient concentration tion in t

270599S

Degree of destruction in% after 2 days

0.1 0.01

100 0

OCF.

(3)

0.1 0.01

100 100

OCP.

(D

0.1 0.01

100 100

OCF.

(8th)

0.1 0.01

100 100

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Table B (continued) (plant-damaging mites)

Tetranychus test

Active ingredients

Active ingredient concentrate tion in%

Degree of destruction in% after 2 days

OCHF;

(5) O, t 0.01

100 1OO

0-P.

> °° 2 ^Η 5

SCF.

(11) 0.1 O, O1

1OO 1OO

(4) 0.1 0.01

100 1OO

S 0-P

^ pC ₃ H ₇ -ISO

CF.

(18) 0.1 0.01

100 100

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Table B (continued) ** (plant-damaging mites)

Tetranychus test

Active ingredients active ingredient killing

concentration in% tion in% after 2 days

S.OC, H - iso
O-P 0.1
0.01 100
100 7 CH
ö Λ
• n ^ xN- ^ NVoCHF ₂
0 0.1
0.01 100
100 S.
_O _ "^ OC ₃ H_-iso
JL ^V CH (15)
»V ^ N- ^ ^ VOCF ₂ -CHF ₂
0 ^ = ^

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Example C

for Diptera test animals: Aedes aegypti

Solvent: acetone

2 parts by weight of active ingredient are taken up in 10OO parts by volume of solvent. The solution thus obtained is with further solvent diluted to the desired lower concentrations.

2.5 ml of the active ingredient solution are pipetted into a Petri dish. A filter paper with a diameter of about 9.5 cm is located on the bottom of the Petri dish. The Petri dish remains open until the solvent has completely evaporated. Depending on the concentration of the active ingredient solution, the amount of active ingredient per m ^{2 of} filter paper is different. Then about 25 test animals are placed in the Petri dish and covered with a glass lid.

The condition of the test animals is continuously monitored. The time that is required for a 100% igen is determined knock down effect is necessary.

Test animals, active ingredients, active ingredient concentration and times at which there is a 100% knock-down effect, leave from the following table C:

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Table C.

for Diptera) Aedes aegypti

Active ingredients

Active ingredient ^{concentration of the LT} ioo solution in%

0-P

O (known)

0.02

3 "= 0%

(known)

C ₂ H ₅

"OCH

'2 * 5

0.02 0.02

3 ^h = 0%

120 ¹

θ £ * ^Α

OCF.

0.02

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Active ingredients

Table C (continued) TeSt for Diptera)

Aedes aegypti

Active ingredient concentration of the , Solution in%

LT

^ _M (11) 0.02

S-CF,

12O ¹

• CH,

OA

'O ^ CHF,

(12) 0.02

(13) 0.02

O-CF ₀ -CHF, * \ / 2 2

120 '

(OC ₂ H ₅ )

(17) 0.02

OCF ₂ -CHF ₂

3 "= 60%

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Table C (port setting) (LT ₁₀ _ test for dipteras)

Aedes aegypti

Active ingredients active ingredient ^{con- LT} ioo

concentration of the solution in%

S.

Il

OP (OC ₂ H ₅ )

(20) 0.02 120 '

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Manufacturing examples

Example 1;

A mixture of 27.2 g (0.1 mol) 1- (4-trifluoromethoxyphenyl) -3-hydroxy-1,6-dihydropyridazinone (6), 2o.7 g (0.15 mol) potassium carbonate, 300 ml methyl isobutyl ketone and 15.9 g (0.1 mol) of O-ethyl methanthionophosphonic acid ester chloride is stirred at 45 ° C. for 3 hours. The reaction mixture is then cooled to room temperature and shaken twice with 300 ml of water each time. The organic phase is separated off, dried over sodium sulfate and freed from the solvent in vacuo. The residue is distilled off. This gives 29.8 g (76 % of theory) of 0-ethyl-0-Q- (4-trifluoromethoxyphenyl) -l, 6-dihydropyridaz (6) on (3) yl] methanthio onophosphonic acid ester in the form of a brown oil with the refractive index n, j ^O : I, 54o2.

The following compounds of the formula

RO R ¹

getting produced:

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game
No. R. R ¹ R ² X Y ötexiuuy
of the sub
stitu-
ten YR ² yield
( % of
Theory) Physical.Data
(Refractive index;
Melting point ⁰ C) 1.5251 842 2 C ₂ H ₅ C ₂ H ₅ O CFj S. O 4th 76 4 ° ' 1.5357 3 C ₂ H ₅ C ₂ H ₅ CFj S. O 4th 79 n ² °: 1,534ο
1.5642 8098 ' 4th
5 iso-CjHy
C ₂ H ₅ CHj
CHj CFj
CHF ₂ CO CO O
O 4th
4th 79
76 n ² °: 1.5458 CJ
• Ν »
O I.
N>
CTl
I. 6th C ₂ H ₅ CHj CF ₂ -CHFCl S. O 4th 55 n ²²
n _D. I, 54o2 ISJ
CO 7th iso-CjHy CHj CF ₂ -CHFCl S. O 4th 53 _n 22.
ⁿ D * 1.5328 ö C ₂ H ₅ CHj CFj S. O 3 58 n ²² 1.5527 9 iSO-CjHy CHj CHF ₂ S. O 4th 66 "22.
ⁿ D * 1.5575 Io C ₂ H ₅ C ₂ H ₅ CHF ₂ S. O 4th 66 "22.
ⁿ D * 1.5617 11 C ₂ H ₅ CHj CFj S. S. 4th 47 1.5638 12th C ₂ H ₅ CHj CHF ₂ S. O 3 59

position

• J at
game
No. R C ₂ H ₅ R ¹ R ² X Y of the sub
stitu-
ten YR ² 3 yield
(% of
Theory) Physika ^ .Data
(Refraction index;
Melting point ⁰ C) O OO IsO-C ₃ H ₇ 4th KJ 13th ISO-CjH ₇ CHj CF ₂ -CHF ₂ S. 0 4th 4th 5o n ²¹ : 1,533o 14th C ₂ H ₅ CHj CHF ₂ S. 0 4th 51 ng ¹ : 1.5568 15th C ₂ H ₅ CHj CF ₂ -CHF ₂ S. 0 4th 48 ng ² : 1.5259 K) 16 iso-CjE, C ₂ H ₅ CF ₂ -CHF ₂ S. 0 4th 55 ng ² : 1.53oo O KJ
«J 17th C ₂ H ₅ C ₂ H ₅ O CF ₂ -CHF ₂ S. 0 4th 60 ng ² : 1.5198 co
co
Cr 18th C ₂ H ₅ CHj CFj S. S. 31 87 19th C ₂ H ₅ CFj S. S. 5o ng ² : 1.5612 2o C ₂ H ₅ O CFj S. S. 48 ng ² : 1.5512

The substituted pyridazinones of the formula (III) to be used as starting materials for the preparation of the compound of the formula (I) according to the invention can, for. B. as follows getting produced:

To a solution of 133 g (o.75 mole) of 4-trifluoromethoxyaniline in 3oo ml concentrated hydrochloric acid and 3oo ml of water is added dropwise at ο - 5 ⁰ C, a solution of 68.3 g of sodium nitrite in 135 ml water. After the addition is complete, the reaction mixture is allowed to flow at 5-10 ° C. to a solution of 45o g of tin chloride hydrate in 45o ml of hydrochloric acid. After half an hour, the precipitated salt is filtered off with suction, dissolved in 900 ml of hot water and the solution is filtered. 73.5 g (0.75 mol) of maleic anhydride are then added to the filtrate at 95-10.degree. C. and the mixture is subsequently stirred at 100.degree. C. for 1 hour. The precipitated product is filtered off with suction at 80 ° C., washed with warm water and then dissolved in dilute sodium hydroxide solution. The filtered solution is acidified with hydrochloric acid, then the product which has crystallized out is filtered off with suction and washed with water. 99 g (49 % of theory) of 1- (4-trifluoromethoxyphenyl) -3-hydroxy-1,6-dihydropyridazinone (6) are thus obtained in the form of a beige powder with a melting point of 243.degree.

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The following compounds of the formula

HC

(III)

YR ²

getting produced:

position

the sub-yield melting point

ρ2 _Y stitu- ( % of ⁰ C

_ ten YR ² theory)

CF ₃ 0 3 15 185

CF ₃ S 4 32 231

CHF ₂ 0 4 34 241

CF ₂ -CHF-Cl 0 4 27 227

CHF ₂ 0 3 31 161

CF ₂ -CHF ₂ 0 4 59 243

CHF ₂ S 4 27 217

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Claims (8)

Claims [1. Pyridazinon (thiono) phosphorus (phosphonic) acid ester of ^ 'For formula Ϊ / OR In which R for alkyl, R ¹ for alkyl or alkoxy, R ^{2 represents} haloalkyl and X and Y are the same or different and represent oxygen or sulfur. 2. Process for the preparation of PyrIdazlnon (thlono) phosphorus (phosphonic) acid esters of the formula (I), characterized in that one (thiono) phosphorus (phosphonic) acid ester halides of the formula (II) 5 / OR (ID In which Le A 17 842 - 30 - 809833/0297 ORIGINAL INSPECTED • 3 · 27ÜS995 R, R and X have the meaning given in claim 1 and Hai represents halogen, preferably chlorine, with 3-hydroxy-1,6-dihydropyridazinones of the formula (III) ₉ (HD YR ^Z in which R and Y have the meaning given in claim 1, optionally in the form of the alkali, alkaline earth or ammonium salts or optionally in the presence of one Acid acceptor and optionally reacted in the presence of a solvent. 3. Insecticidal and acaricidal agents, characterized by a content of compounds according to claim 1. 4. methods of combating insects and arachnids, characterized in that compounds according to Claim 1 are allowed to act on the said pests or their habitat. 5. Use of compounds according to Claim 1 for combating insects and arachnids. Le A 17 842 - 31 - 309833/0297 6. Process for the preparation of insecticides and acaricidal agents, characterized in that one compounds according to claim 1 mixed with extenders and / or surface-active agents. 7. 3-Hydroxy-1,6-dihydropyridazinones of the formula YR ² (III) in which 2
R and Y have the meaning given in claim 1. 8. Process for the preparation of 3-hydroxy-1, 67-dihydropyridazinones of the formula (III), characterized in that anilines of the formula (IV) (IV) in which 2
Y and R have the meaning given in claim 1, are diazotized, the diazonium salts obtained are reduced to the hydrazines and these are reacted with maleic anhydride. Le A 17 842 - 32 - «09833/0297